Polyene coloring compositions

ABSTRACT

Conjugated polyene dialdehyde compounds useful as coloring agents for foodstuffs, pharmaceutical preparations and cosmetic preparations.

United States Patent [191 Gutmann et al.

[54] POLYENE COLORING COMPOSITIONS [75] Inventors: Hugo Gutmann; UlrichManz, both of Reinnach; Ulrich Schwieter, Arlesheim, all of Switzerland[73] Assignee: Hoffmann-La Roch Inc., Nutley,

[22] Filed: Jan. 4, 1971 [21] Appl. No.: 103,880

Related U.S. Application Data [62] Division of Ser. No. 608,487, Jan.1], 1967, Pat. No.

[52] U.S. Cl ..424/333, 99/140 [5 1] Int. Cl. ..A6lk 27/00 [58] Field ofSearch ..424/333; 99/140 [56] References Cited OTHER PUBLICATIONSYamaguchi, Bull Chem. Soc., Vol. 30, 1957, pp. 979-983.

51 Jan.30, 1973 Primary ExaminerStanley J. Friedman Attorney-Samuel L.Welt, Jon S. Saxe, Bernard S. Leon, William H. Epstein and George M.Gould [57] ABSTRACT Conjugated polyene dialdehyde compounds useful ascoloring agents for foodstuffs, pharmaceutical preparations and cosmeticpreparations.

6 Claims, No Drawings POLYENE COLORING COMPOSITIONS CROSS REFERENCE TORELATED APPLICATION This application is a division of U.S. Pat.application Ser.No.608,487,filedJan.11,1967 now U.S. Pat. No. 3,577,464,May 4,1972.

BACKGROUND OF THE INVENTION This invention relates to coloring agentsand the use of these coloring agents in coloring materials such asfoodstuffs, pharmaceuticals and cosmetics. This invention also relatesto a method of producing these coloring agents including intermediatesin the preparation thereof.

Of the pigments of natural or synthetic origin which are suitable forcoloring foodstuffs, B-carotene and the apocarotenals derived fromnatural pigments have been found to be particularly useful. However,various disadvantages impose a limit on the general use of thesepigments. This is seen by the fact that the color tones achieved withthese pigments lie within a relatively narrow range which extends fromyellow-orange to yellow red. Intermediate tones, can of course, beobtained by mixing various components. However, such mixtures ofpigments are not color-constant when, as is frequently the case, theindividual components are unstable or differentially stable. Thesepigments also vary their color with increasing dilution. In the case ofcarotene, for example, an undesirable color-shift toa pale yellow isobserved with decreasing concentration. The desired saturated tints mayoften only be achieved by high concentrations, which are associated withhigh costs and are therefore uneconomical.

SUMMARY OF THE INVENTION In accordance with this invention, it has beenfound that when polyene dialdehyde compounds of the formula:

itifii mii wherein X is an integer from to 1, Y is an integer from 0 to3 with the proviso that the sum of X and Y is an integer of at leastone, or mixtures thereof when incorporated into foodstuffs, includingbeverages, pharmaceutical preparations and cosmetic preparations imparta wide variety of colors to these materials and do not possess many ofthe disadvantages which are presentwith regard to B-carotene and theapocarotenals derived from natural pigments. The dialdehyde compounds inaccordancewith this invention range from C] 14 dialdehydes to C 44dialdehydes and range in color from yellow to violet. The lower membersof thisseries of compounds are colored intensive yellow, orange andraspberry red and the higher members are colored ruby red and violet.Hence, these new compounds extend the very small range of foodstuffpharmaceutical and cosmetic colors in a manner that has not beenachieved by the known coloring compounds.

Furthermore, these compounds have a high degree of stability and aredistinguished from other food coloring substances with related colorproperties by the fact that their pigment or coloring character is notinfluenced by the concentration of the compound in a solution. Solutionsof these substances or compounds surprisingly retain their tint unvariedeven when these compounds are greatly diluted. The compounds of formulal are therefore suitable in an outstanding manner for coloringfoodstuffs, pharmaceutical and cosmetic preparations.

In accordance with this invention, it has been found that two newcompounds which fall under the compounds of formula I above, i.e.,4,8,l2,l7,2l,25-hexamethyl-octacosa-tridecaene-(2,4,6,8,l0,l2,14,l6,l8,20,22,24,26)-dial-(l,28), (a C34 dialdehyde) and2,6,l0,l4,l9,23,27,3l-octamethyl-dotriaconta-pentadecaene-(2,4,6,8,l0,l2,l4,l6,18,20,22,24,26,28,30)-dial-(1,32 (a C40 dialdehyde)respectively impart a violet color to foodstuffs, pharmaceuticals andcosmetics into which these compounds are incorporated. Among othercompounds within formula I,4,9-dimethyldodeca-pentaene-(2,4,6,8,l0)!dial-(1,12), (C14 dialdehyde)imparts to foodstuffs, pharmaceuticals, cosmetics an intensivelylemon-yellow pigment, whereas2,6,10,15,l9,23-hexamethyl-tetracosa-undecaene-(2,4,6,8,l0,l2,l4,16,l8,20,22)-dial-(1,24),(C 30 dialdehyde) imparts a red color.

Furthermore, in accordance with this invention, the coloring agents offormula I above are prepared by reacting the phosphonium salt of theformula:

wherein R, R and R"" are selected from the group consisting of arylradicals containing from six to 16 carbon atoms, aralkyl radicalscontaining from seven to 16 carbon atoms and alkyl radicals containingfrom one to 16 carbon atoms, Z is an anion of a mineral acid and B is aconjugated olefinic radical containing from four to 14 carbon atoms andat least one methyl side chain, with an organic aldehyde of the formula:

wherein R, is a lower alkyl radical and B, is a conjugated olefinicradical containing from four to 14 carbon atoms and at least one methylside chain, and thereafter hydrolyzing this reaction product to form adialdehyde of the formula:

wherein B and B, are as above. This dialdehyde can further react, ifdesired, with at I least 2 moles of the phosphonium salt of the formula:

14 carbonatoms and at least one methyl side chain,

or, according to anotheralternative, with a vinyl ether or propenylether to produce a conjugated polyene dialdehyde of a high molecularweight.

DETAlLED DESCRIPTION The coloring agents. of formula 1 above, inaccordance with this invention, can be used to color any conventionalfoodstuff including beverages, fruits, vegetable preserves, marmalades,cream foods, confectionary, edible fats, cheese, fish products; pasta,soup powders, etc: Any conventional pharmaceutical preparation can becolored by compounds of formula 1. Among the typical pharmaceuticalpreparations which can be colored in accordance with this invention areincluded dragees, suppositories, gelatin capsules and syrups. Also anyconventional cosmetic preparation can be colored with the compounds offormula 1 above. Among the conventional cosmetic preparations which canbe colored in accordance with this invention are included, toothpaste,skin creams, lipsticks and non-alcoholic mouthwashes.

In coloring materials such as foodstuffs, cosmetic and pharmaceuticalpreparations, the compounds of formula 1 above should be added to thematerial in an amount sufficient to impart a color to the material.Generally, it is preferred that the foodstuff, pharmaceutical andcosmetic preparation contain from about 0.0000001 parts by weight toabout 0.1 parts by weight of compound of formula l above based on theweight of the foodstuff, pharmaceutical-and cosmetic preparation. it issuitable to make the amount of compounds of formula 1 to be addeddependent on the nature of the preparations to be colored. Thus, forcoloring foodstuffs, it is advantageous to add from about 0.0000001parts by weight to about 0.0001 parts by weight of compound of formula Ibased on the weight of the preparation (e.g. about 0.000002 parts byweight to about 0.000005 parts by weight are used for coloringbeverages, such as carbonated orange beverages, about 0.00001 parts byweight to about 0.000025 parts by weight are used for coloring icecreams, confectionary etc. and 0.00001 parts by weight to about 0.00005parts by weight are used for coloring yoghurts). in the cosmetic fieldpreferably about 0.0000001 parts by weight to about 0.05 parts by weightof compound of formulal are used based on the weight of the cosmeticpreparation (e.g. from about 0.001 parts by weight to about 005 parts byweight are used for coloring lipsticks and from' about 0.0000001 partsby weight to about 0.00002 parts by weight are used for coloring creams,such as skin creams, toothpaste etc.). Pharmaceutical preparations, suchas suppositories and syrups preferably contain from about 0.000005 partsby weight to about 0.001 parts by weight based on the weight of thepreparation. In case of coloring drag'ees, the coating suitably containsfrom about 0.001 mg to about 0.1 mg of compound of formula 1 per cmsurface of the dragees. Although greater amounts than the parts byweight of the compound of formula I specified above can be incorporatedinto the foodstuff, pharmaceutical or cosmetic preparation, however,these high amounts are seldom utilized since no additional benefits, asfaras color is concerned, is obtained by utilizing such large amounts ofthe compounds of formula 1 above. 1

The polyene compounds of formula I can be employed for coloringfoodstuffs, pharmaceutical and cosmetic preparations both in theoriginal crystalline form and in a particular water-soluble form.

The polyene compounds of formula l'above can chiefly be used in thecrystalline form for coloring fats and oils, as well as fat-containingsubstances such as, for example, marzipan, suppositories, lipsticks. Thepolyene compounds of formula 1 above, can, for example, be dissolved inoils without further ado. Prior to the addition of the pigment, hard orsoft fats are conveniently liquified by heating. Brushable fats may alsobe colored by kneading-in an oil pigment-solution. Marzipan, which forexample, is thoroughly kneaded with a solution of the polyene compoundof formula 1 in almond oil, can also be colored in the same way.Coloredsuppositories and lipsticks can, for example, be manufactured insuch a way that the polyene compound used as the pigment is stirred intothe liquified carrier mass prior to filling into the molds.

For coloring fat-poor or fatless substances, there is generally used awater-dispersible form of the polyene compounds of formula 1. Thepreparation of these compounds in water-dispersible form can be carriedout by any of the techniques disclosed in U. S. Pat. No. 2,861,891,Bauernfeind et al. and U. S. Pat. No. 3,110,598, Muller et al. Theseinclude dissolving the polyene compounds of formula I in a suitablesolvent, homogenizing the solution (together with a stabilizer and asolubilizing or emulsifying agent if required, as well as with an animalor vegetable fat if desired) with water in the presence of a protectingcolloid and evaporating the emulsion formed to dryness under reducedpressure.

Any conventional organic solvent capable of dissolving the compound offormula 1 above, can be utilized. These solvents include volatilehalogenated hydrocar- .bons such as, for example, chloroform, carbontetrachloride, methylene chloride, etc. Any conventional antioxidativelyactive stabilizers can be utilized. These antioxidants includetocopherols, 2,6-ditertbutyl-4-hydroxytoluene [Bl-1T],butyl-hydroxyanisole [B- H The salts of fatty acid esters of ascorbicacid (e.g. th sodium salt of ascorbyl palmitate), interalia, have beenfound to be active as solubilizing agents. Any of the conventionalsolubilizing agents can be utilized in accordance with this invention.Concerning emuls'ifying agents, any. conventional emulsifying agent canbe utilized in accordance with this invention. The polyoxyethylenederivatives of sorbitan anhydrides partially este'rified withfatty'acids [Tweens] or non-ionogenic derivatives'of fatty compoundswith polyoxyethylene derivatives [Cremophores] are, for example, usable.The protecting colloids in which the compounds of formula I areemulsified or dispersed includeany of the conventional water solublegelable colloids. Gelatin, dextrin, pectin, tragacanth, guar-(especially in the presence of saccharose, glycerin, sorbitol), have,for example, been found to be useful as protecting colloids. The colorbrilliance of the aqueous solutions can be increased by the addition ofany animal fat (e.g. beef tallow or vegetable oil (e.g. groundnut oil).

The C. 14 to C 44 dialdehydes of this invention ca be prepared bybuilding up the molecule through chain-lengthening of suitablealdehydes. The lowest member 4,9-dimethyl-dodeca-pentaen'e-(2,4,6,8,10)-dial-(l,l2) [C 14 -dialdehyde] is obtained by the condensation of2,7-dimethyl-octa-triene-(2,4,6)-dial-(1,8 )-diacetal with two moles ofvinyl ether.

O R--O-CHz-A-CHO 1].

desired, after its conversion into a halogeno compound, with a phosphinecompound of formula X, as in step (1), in carrying out the reaction ofstep (I), compounds wherein A is a conjugated four to 14 carbon radicalhaving one acetylene linkage therein and having at least one,preferablyfrom one to six methyl side chains, B is the same as A withthe one acetylene linkage reduced to an olefinic linkage, R is ahydrogen or lower alkyl radical containing from one to seven carbonatoms, R is a lower alkyl radical containing from one to seven carbonatoms, R', R", R being an aryl radical containing six to 16 carbonatoms, an aralkyl radical containing from seven to 16 carbon atoms or alower alkyl radical containing from one to seven carbon atoms and Z isan anion of a mineral acid, e.g.Br. Cl-, 1- and l-lSO,.

The reduction of compounds of the formula II above to compounds offormula III above can be effected by catalytic hydrogenation in thepresence of a catalyst which selectively reduces only the triple bond(acetylene linkage) to a double bond. For example, compounds of formulall above can be catalytically hydrogenated, in an inert solvent such asethyl acetate, toluene or petroleum ether, in the presence of aselective hydrogenation catalyst, e.g., a palladium-lead catalyst in thepresence of quinoline, of the type disclosed in the publicationHelvetica Chimica Acta, 35,446 (1952).

The conversion of compounds of the formula III above to compounds of theformula IV-b above, is carried out by first hydrolyzing the esterlinkage in the compounds of formula lll above to form the hydroxycompound of formula lV-a above which is oxidized to thealdehyde offormula IV-b. During this procedure, the aldehyde group in formula Illabove is protected during the oxidizing step (e) by means of its beingconverted to an acetal group anytime before oxidation.

Compounds of formula iii are converted into compounds of the formula V-aby first hydrolyzing the ester group in the compounds of formula III tothe hydroxy compound of formula V and thereafter reacting the hydroxycompound of formula V above, if

of formula V or halogeno derivatives thereof are reacted with aphosphine of the formula X in an inert solvent (such as, for example, alower alkanol such as methanol or ethanol) in the presence of a protondonor or with an acid addition salt of the phosphine of formula X or adiarylmonoalkyl phosphine. Proton donors which can be employed in theabove process include inorganic acids such as hydrohalic acids orsulfuric acid. In this manner, the compounds of the formula V-a areformed.

During the reaction of step (1), it is preferable to first form theacetal of compound V, by means of utilizing a conventional acetalforming agent, so as to protect the aldehyde group of compound V duringits reaction with the I phosphine of formula X. In this case the acetalfunctional group would be converted to the cormethanol and benzene. Thereaction is conducted in the presence of a strong base, such as analkali metal hydride, e.g., sodium hydride, potassium hydride, an alkalimetal amide, e.g., sodium amide, alkali metallower alkoxide, preferablysodium methoxide, or a solution of an alkali metal hydroxide in a loweralkanol,

e.g KOH in methanol. This reaction can be carried out at roomtemperature. However, temperatures as high as the reflux temperature ofthe solvent or as low as the freezing point of the solvent can beeffectively employed. In carrying out the reaction of step (g), one moleof the compounds of formula lV-b can be reacted with one mole of thecompound of formula V-a if desired. However, a molar excess of thecompound offormula lV-a or the compounds of formula V-a can be utilized.

Compound Vl can be converted to the dialdehyde compounds of thisinvention (compounds of formula Vll above) by any conventional acidhydrolysis to hydrolyze the acetal radical to the correspondingaldehyde. If desired, the compounds of formula Vll above can be furtherchain-lengthened by reacting the compound of formula Vll above with thephosphonium salt of compound V-a above as in step (i). This reaction canbe carried out in the same manner as step (g) except that at least twomoles of the compound of formula V-a or of an acetal thereof should beutilized per mole of the compounds of formula Vll above. Alternatively,compounds of formula Vll above can be chainlengthened by reaction with avinyl ether or a propenyl ether, preferably a lower alkyl ether.

ln carrying out the reaction of step (g), a phosphonium salt containingthe same B-radical as the B-radical in compound lV-b can be utilized.However, if desired, the phosphonium salt containing a differentB-radical than the B-radical in compound lV-b can be utilized incarrying out step (g) In carrying out step (i), the phosphonium saltthat is utilized can be the same phosponium salt as that used in step(g) or a different phosphonium salt than is utilized in step Thisinvention is further illustrated by the following examples which areillustrative but not limitative thereof.

EXAMPLE 1 Preparation of 2,6,1 l,l5tetramethyl-hexadeca-heptaene-(2,4,6,8,10,l2,14-dial-( 1 ,l6) [C 20dialdehyde].

A. Preparation of 8,8-dimethoxy-3,7-dimethyl-octatrien-(2,4,6)-al-l.

All trans 8,8-dimethoxy-3,7-dimethyl-octa-trien- (2,4,6)-al-(l can bemanufactured in an advantageous manner as follows:

7l g. of 8-acetoxy-2,6-dimethyl-octa-trien-(2,4,6)- al-(l) are suspendedin 15 ml. of-methanol and 41 ml. of orthoformic acid trimethyl esterand, after the addition of 3.5 ml. of a 1 percent solution ofptoluenesulphonic acid in methanol, stirred at 20-25 C. for4 hours; Theacetoxy acetal [absorption maximum (in petroleum ether) 276 [1.1present'in the clear solution is not isolated, but is directlyalkalinesaponified. A solution of 37.7 g. of sodium hydroxide in 34 ml.of water'and 180 ml. of methanol is added dropwise thereto with stirringat -5 C. within 20 minutes. The reaction mixture is further stirred atl0 C. for minutes, immediately thereafter poured into 2.5 liters ofice-cold 5 percent by weight potassium hydrogen carbonate solution andextracted twice with ether (500 and 800 ml.). The ether phase iswashedtwice with fresh potassium hydrogen carbonate solution and dried overpotassium carbonate.

The hydroxy acetal [absorption maximum (in petroleum ether) 276 p.)containing ether solution is subsequently treated with 300 g. ofmanganese dioxide and stirred or shaken at l0 C. for 60 hours, thenfiltered and evaporated. The residual oil is taken up in 10 ml. ofpetroleum ether (boiling range .40- 45 C.) and I cooled in the ice-bathfor 6 hours. The orange-yellow all trans8,8-dimethoxy-3,7-dimethyl-octa-trien-(2,4,6

)-al-(l) crystallizing out melts at 5758 C. after recrystallization frompetroleum ether: absorption maxima (in petroleum ether) 300 (shoulder),313,327 .1.; E 1380, 2,000, i780.

B. Preparation of (3,7-dimethyl-8-oxo-octatrien-(2,4,6)-yl)-triphenyl-phosphonium bromide.

A mixture of 10.5 ml. of dimethylformamide and 45 ml. of methylenechloride is treated with stirring at 20 C. with 6.5 ml. of phosphoroustribromide and thereupon within 20 minutes with a solution of 16.6 g. of8-hydroxy-2,6-dimethyl-octa-trien-(2,4,6)-al-(l) in 25 ml. of methylenechloride. The reaction mixture is stirred at l0 C. for 1 hour, thenpoured in ice-water and extracted with 300 ml. of ether. The etherextract is washed twice with ice-water, three times with icecold 10percent potassium hydrogen carbonate solution and twice with ice-water,briefly dried over sodium sulphate and immediately evaporated underreduced pressure at 20 C. The residual8-bromo-2,6-dimethylocta-trien-(2,4,6)-al-( l) crystallizes aftertrituration with a little ether. M.p. 68-70 C; absorption maximum (inpetroleum ether) 3 ll it. Without further purification, the unstablecompound is immediately dissolved in 50 ml. of methylene chloride andtreated with 26 g. of triphenyl-phosphine. In doing so, the solutionwarms up to boiling. After i to lyhours, 200 ml. of acetic acid ethylester are slowly added while scratching with a glass rod. The(3,7-dimethyl-8-oxoocta-trien-(2,4,6)-yl)-triphenyl-phosphonium bromidecrystallizing out is filtered off in the cold after standing for 12hours. M.p. 203-205 C; absorption maximum (in ethanol) 315 mu; E,,,,,,'=970.

C. Preparation of dialdehyde.

- 60 g. of (3,7-dimethyl-8-oxo-octatrien-(2,4,6)-yl)-triphenyl-phosphonium bromide in 160 ml. of abs. methanol are treatedwith 20 ml. of orthoformic acid trimethyl ester and a solution of 0.1 g.of ptoluenesulphonic acid and 0.1 ml. of percent phosphoric acid in 20ml. of abs. methanol and allowed to stand at room temperature for 18hours. The reaction mixture is thereafter treated with 2 ml. of pyridineand subsequently simultaneously with a solution of 21 g. of8,8-dimethoxy-3,7 dimethyl-octa-trien-(2,4,6)-all) in 100 ml. of abs.benzene and a sodium methylate (2,4,6,8,l0,l2,l4)-is dissolved in 300ml. of acetone 7 and, after the additionof 15ml. of l-N sulphuric acid,heated to boiling for 30 minutes. The 2,6,l l,l5-tetramethyl-hexadeca-heptane'-( 2,4,6 ,8 ,l0,l 2,14)- dial-(l,l6) whichseparates out melts at l-l9l C. after recrystallization from' aceticacidethyl ester;

violet, metalically shining leaflets; absorption maxima (inchloroform)267, 455, 483 mu; 13. 580, 3970, 3840. r 1

By extraction with methylene chloride and isomerization by exposure tolight in the presence of iodine, further fractions of this aldehyde maybe obtained from the filtrate.

According to the same mode of procedure described above, there canfurther be manufactured:

from 2 mol of (3-methy1-6-oxo-hexa-dien-(2,4)-y1)- triphenyl-phosphoniumbromide and 1 mole of 2,7- dimethyl-octa-trien-(2,4,6)-dial-( 1,8) therewas produced 4,8,13,17-tetramethyl-eicosa-nonaene-(2,4,6,8,10,l2,l4,16,18-dial-(1,20) [C -diaIdehyde]; violet needles:m.p: 226-227 C; absorption maxima: (in chloroform) 300, 492, 523 mu; E660, 3750, 3460, from 2 mole of (3,7-dimethyl-8-oxo-octa-trien-(2,4,6)-y1) triphenyl-phosphonium bromide and 1 mole of2,7-dimethyl-octa-triene-(2,4,6)-dia1-(1,8) there was produced2,6,l0,15,l9,23-hexamethyl-tetracosaundecaene-(2,4,6,8,10,12,l4,16,18,20,22)-dial-(1,24) [C -dialdehyde]; violet needles; mp 233-235 C.; absorption maxima:(in chloroform) 329,520,552 mu; E 745, 3,590, 3,050, from 2 mole of(3,7- dimethyl-l-oxo-deca-tetraen-(2,4,6,8)-yl)-triphenylphosphoniumbromide and 1 mole of 2,7-dimethyl-octatriene-(2,4,6)-dia1-( 1,8), therewas produced 4,8,12,17,21,25-hexamethyl-octacosa-tridecaene-(2,4,6,8,10,12,14,l6,18,20,22,24,26)-dia1-(1,28)[C dialdehyde]; violetneedles; mp. 239240 C. absorption maxima: (in chloroform) 356, 541 mp;E,,,,,"' 760, 3,060, from 2 mole of(3,7-dimethyl-8-oxo-octatrien-(2,4,6)-yl)-triphenyl-phosph0nium bromideand 1 mole of 2,6,1l,15-tetramethyl-hexadeca-heptaene-(2,4,6,8,10,12,14)-dia1-(1,16), there was produced2,6,10,14,19,23,27,31octamethyl-dotriaconta-pentadecaene-(2,4,6,8,10,12,l4,16,18,20,22,24,26,28,30)-dia1-(1,32) [C -dialdehyde]; violet crystals; m.p. 261263 C.;absorption maxima (in chloroform) 380, 556 mp;E =8l0,2770.

Examples 2 and 3 illustrate the preparation of starting materials forthe above which are not known.

EXAMPLE 2 Preparation of [3-methyl-6-oxo-hexa-dien-2,4 yl]-triphenyl-phosphonium bromide.

(3-methyl-6-oxo-hexa-dien-(2,4)-yl)-tripheny1- phosphonium bromide canbe manufactured in an advantageous manner as follows:

42.5 g. of 6-hydroxy-4-methyl-hexa-dien-(2,4)-al- (l) is reacted with21.5 ml. of phosphorous tribromide and extracted with ether in themanner described in part B of Example 1. The ether extract whichcontained the unstable 6-bromo-4-methyl-hexadien-(2,4)-al-(1) is,however, not evaporated but remains in a cold state and is treated witha solution of 88 g. of triphenyl-phosphine in 100 ml. of methylenechloride. The (3-methyl- 6-oxo-hexa-dien-(2,4)-yl)-triphenyl-phosphoniumbromide, initially oily, crystallized after trituration. Thisphosphonium bromide salt separates out after standing at roomtemperature for 2 hours. The salt is recrystallized from a mixture of350 ml. of methylene chloride and 1.1. liters of acetic acid ethylester. M.p. 200202 C. (dec.); absorption maxima (in ethanol) 268(shoulder), 274 mu; E =610, 630.

EXAMPLE 3 Preparation of [3,7-dimethyl-l0-oxo-deca-tetraen- (2,4,6,8)-yl]-triphenyl phosphonium bromide.

A. Preparation of 10-acetoxy-4,8 dimethyl-decatrien-(2,4,8)yn-(6)-al-1.

280 g. of 8-acetoxy-l,1-diethoxy-2,6-dimethyl-octadien-(2,6)-yne-(4) wasdissolved in 300 ml. of benzene and treated dropwise at 30-35 C.simultaneously with g. of ethyl vinyl ether and 50 ml. of a 10 percentsolution of anhydrous zinc chloride in acetic acid ethyl ester. Thereaction solution is left to stand at room temperature for 18 hours.Subsequently, 75 g. of anhydrous sodium acetate in 750 ml. of 87 percentacetic acid are added. Then it is heated to C., held at this temperaturefor 4 hours, poured on 5 liters of ice-water and extracted with ether.The ether extract is washed with sodium hydrogen carbonate andneutralized with water, dried over sodium sulphate and evaporated. Theresidue is dissolved in ml. of ether and cooled to -20 C. Thel0-acetoxy-4,8-dimethyl-deca-trien-(2,4,8 )-yn-(6)-a1-( l) whichcrystallizes out melts at 3132 C. U.V. maxima (in petroleum ether) 310(shoulder), 325, 342 mp;E,,,,,=1350,1590, 1355.

B. Preparation of l0-acetoxy-4,8-dimethyl-decatetraen-(2,4,6,8)-al-( l57 g. of 10-acetoxy-4,8-dimethyl-deca-trien-(2,4,8)- yn-(6)-a1-( l weredissolved in 300 ml. of toluene and, after the addition of Lindlarcatalyst [Helv.-Chim.- Acta 35 (1952) 446] and 0.5 ml. of quinoline,hydrogenated up to the uptake of 1.05 equivalents of hydrogen. Thecatalyst is filtered off. The filtrate is successively washed with 0.5-Nsulphuric acid, potassium hydrogen carbonate solution and water, driedover sodium sulphate and treated with a solution of 0.2 g. of iodine in50 ml. of toluene. The toluene solution is left to stand atroomtemperature for 18 hours. It is subsequently successively washedwith a 5 percent sodium thiosulphate solution and water, dried oversodium sulphate and evaporated under reduced pressure. The residue istaken up in 30 ml. of isopropyl alcohol and cooled to -20 C. The10-acetoxy-4,S-dimethyl-decatetraen-(2,4,6,8)-al-( 1) which crystallizesout melts at 6466 C. U.V. maxima (in petroleum ether) 318, 333, 350 mu;E,,,,,'= 1790, 2,860, 2,700.

C. Preparation of 10-hydroxy-4,8dimethy1-decatetraen-(2,4,6,8)-al-l. g

22.3 g. of finely powderedl0-acetoxy-4,8-dimethyldecatetraen-(2,4,6,8)-al (1) are suspended in ml.of methanol and treated with vigorous stirring at 0-2 C. within 15minutes with a solution of 4 g. of sodium hydroxide in 4 ml. of waterand 40 ml. of methanol. The reaction mixture is further stirred at 0 for10 minutes, adjusted at this temperature to pH 7-8 with alcoholichydrochloric acid and evaporated under reduced pressure at ca 30 C. Theresidue was partitioned between methylene chloride and water. Themethylene chloride phase was washed with potassium hydrogen carbonatesolution and water, dried over sodium sulphate and evaporated. Theresidue was dissolved in 1.5 liters of boiling ether. The solution wasconcentrated up to incipient crystallization and cooled to -20 C. The10-hydroxy-4,8-dimethyl-deca-tetraen- (2,4,6,8)-al-(1) formsorange-colored crystals. M.p. 103105 C. [after sublimation: 104-1.5 C.];absorption maxima (in petroleum ether) 319, 334, 351 mp; E,,,,,*=2160,3360, 3170.

D. Preparation of phosphonium salt.

The aldehyde prepared in part C was reacted with phosphorous tribromideand triphenyl phosphine to form[3,7-dimethyl-l0-oxo-deca-tetraen-(2,4,6,8)-yl]- triphenyl-phosphoniumbromide in the manner of part B of Example 1. The melting point of thiscompound l l was 202-204C. (dec); absorption maximum (in ethanol) 354my. E 1060.

Examples 4 through 19 are directed to the use of the compounds offormula 1 above as coloring agents in foodstuffs, pharmaceutical andcosmetic preparations.

EXAMPLE 4 Manufacture of canary-yellow colored dragees 10,000 drageekernels each of 150 mg. are coated white up to a kernel weight of 190mg. with sugar syrup, starch and talc.

30 g. of color preparation containing 300 mg. of the C -dialdehydedisclosed above are soaked with 30 g. of water, combined with a solutionof 330 g. of sugar and 135 g. of water which has been heated to boilingand subsequently cooled to 60-70 C., and homogenized. The yellow coloredsugar solution is applied little by little to the white-coated drageesin the rotating coatingpan, sprayed with cold air. The dragees arepolished in the usual manner. The color layer of one dragee (weight 225mg., diameter 1 cm., thickness 3mm.) contains 0.03 mg. .of C-dialdehyde.

The water-soluble preparation employed as colordonor is, for example,manufactured as follows:

1 g. of a polyene compound of formula l are dissolved in 100 ml. ofchloroform and together with 100 mg. of tocopherol, 2g. of arachis oiland 2 g. of ascorbyl palmitate introduced into a solution of 60 g. ofgelatin, 35 g. of sugar and 0.5 g. of calc. soda in 250 ml. of water andhomogenized. The colored chloroform-con.- taining gelatin emulsion ispoured on a metal sheet and subsequently evaporated in vacuum. The dryproduct is broken into small pieces.

' EXAMPLE 5 Manufacture of lemon-yellow confectionery l g. of commercialfondant mixture is homogene- I ously mixed on a roller frame with asolution of 1.5 g. of color preparation containing 15 mg. of the C-dialdehyde disclosed above in 5 ml. of water. In order to achieve thedesired fluidity of the mass, either invert- EXAMPLE 6 Manufacture oflemon-yellow ice-cream 1 2 g. of colorpreparation containing 20 mg. ofthe C -dialdehyde disclosed above, are dissolved warm in 5 ml. of waterand added to the raw materials (such as cream, milk, sugar,gelatin,aroma-substances) necessary for 1 liter of ice-cream. Alemon-yellow ice-cream is obtained.

EXAMPLE 7 Manufacture of lemon-yellow caramels l.5 g. of colorpreparation containing l5 mg. of the C -dialdehyde, disclosed above, isdissolved in 5 ml. of water and added to 1 kg. of bon-bon mixturetowards the end of the .cooking process or during the subsequentprocessing and homogeneously worked in.

EXAMPLE 8 Manufacture of egg-yellow colored fats and oils 5 mg. of the C-dialdehyde prepared in Example l are dissolved warm in 1 liter of oilor fat, a beautiful egg-yellow coloring being achieved.

EXAMPLE 9 Manufacture of yellow-orange colored pasta 1 kg. of hardwheat-grain is intimately mixed in a mixing drum with 300-350 ml. ofwater in which 0.5 g. of color preparation containing 5 mg. of the C-dialdehyde prepared in Example 1 have been dissolved. The moist spQngymass is brought into the desired form of pasta through suitable nozzlesand dried.

EXAMPLE 10 EXAMPLE 11 Manufacture of orange-red colored suppositories g.of suppository mixtureare heated with l 00 mg. of the crystallized Cdialdehyde prepared in Example 1 up to complete solution of the pigment.a- Tocopherol, BHT, BHA, gallates etc. can be admixed as antioxidants.After working-in the active substance, the orange red fatty-mass ispoured into the usual molds and allowed to cool.

EXAMPLE 12 Manufacture of red colored gelatin capsules 10 g. of colorpreparation containing 100 mg. of the C -dialdehyde prepared in Examplel are dissolved warm in 30 ml. of water and mixed with a hot gelatinsolution consisting of 650 g. of gelatin, 250 g. of glycerin (which canalso be partially replaced by sorbitol or other carbohydrates) and 800g. of water. The gelatin capsules are manufactured in the usual way,according to the clipping or press process, from this gelatin solution.

. EXAMPLE 13 Manufacture of raspberry colored syrups and candied fruitsi Per kg. of syrup or candied fruit, 2 g. of color preparationcontaining 20 mg. of the C -dialdehyde prepared in Example Iare'dissolved warm in 5 ml. of water and added to the syrup or to thecandied fruit mixture towards the end of the thickening process.

EXAMPLE 14 Manufacture of red colored gelatin foods 2 g. of colorpreparation containing 20 mg. of the C -dialdehyde prepared in Example 1are dissolved in 6 ml. of warm water and stirred into 1 liter of thewarm, liquid gelatin solution consisting of the usual ingredients. Thesolution 'is poured into molds and allowed to cool.

The. same amount of pigment powder can also be mixed dry with thegelatin pudding powder sufficient for 1 kg. of prepared gelatin pudding.The pigment particles dissolve, red colored gelatin desserts beingobtained.

EXAMPLE l Manufacture of a reddish pastel-colored daytime cream 1 g. ofcolor preparation containing mg. of the C -dialdehyde prepared inExample 1 is dissolved in 65 ml. of warm water. The solution isemulsified into a salve base which consists of g. of cetyl alcohol andoctadecyl alcohol, 3 g. of spermacetti l g. of butyl stearate, l g. oflanolin, 5 g. of CETlOL, 2.8 g. of COROL, 8 g. of glycerin orpropyleneglycol and 0.5 g. of perfume oil composition.

EXAMPLE l6 Manufacture of a bordeaux-red pudding mixture 2 g. of colorpreparation containing mg. of the C -dialdehyde prepared in Example 1are admixed with the pudding powder which is sufficient for 1 liter ofready-prepared pudding and the mixture is further processed as usual bystirring or boiling up with milk.

EXAMPLE 17 Manufacture of bordeaux-red colored yogurt 2 g. of colorpreparation containing 20 mg. of C -dialdehyde prepared in Example 1 aredissolved warm in 5 ml. of water, mixed with 1 liter of milk andprocessed to give yogurt in the usual manner.

EXAMPLE 18 Manufacture of a bordeaux-red marzipan mixture 10 mg. ofcryst. the C -dialdehyde prepared in Example 1 are dissolved hot in 10g. of almond oil and, still warm, worked manually or by machine into 1kg. of marzipan mixture. ifdesired, the marzipan mixture can also becolored with a water-soluble pigment preparation which, dissolved in alittle water, is mixed wit the marzipan mixture.

EXAMPLE 19 Manufacture of a ruby colored toothpaste 0.5 g. of pigmentpowder containing 5mg. of C -dialdehyde prepared in Example 1 aredissolved in 2 ml. of water and homogeneously worked into 100 g. ofwhite toothpaste of the usual composition. If. desired, the same pigmentpreparation can also be added to the raw materials dissolved in water orconverted into a paste with water.

EXAMPLE 20 This example is directed to preparing 8-acetoxy-2,6-dimethyl-octa-trien-(2,4,6)-al-( l) which is utilized as a startingmaterial in Example 1.

A. Preparation of ether.

175 g. of crude 5-( l-methoxy-l-methylethoxy) 3- methyl-pent-B-en-l-yneare introduced in a rapid stream into a solution of lithium amide inliquid ammonia.

The ammonia-alkaline lithium amide solution can be manufactured asfollows:

0.5 g. of finely divided lithium are introduced with stirring into 600ml. of liquid ammonia. After the addition of 0.5 g. of iron (Ill)nitrate, compressed air is led into the solution for a few seconds. Assoon as the blue color of the solution has disappeared, a further 7.1 g.of

finely divided lithium are added. The evaporating ammonia is condensedin a condenser charged with acetone/dry ice and led back to the reactionmixture. The mixture is stirred until the blue color disappears [15 to60 minutes.]

The dark clear reaction solution is stirred for 90 minutes, then treatedwith 170 ml. of dry toluene and immediately subsequently with 114 g. of3-ethoxy-2- methylacrolein in a rapid stream and further stirred for 30minutes. The mixture is subsequently neutralized by the addition of 80ml. of glacial acetic in 200 ml. of toluene. The acid solution isconveniently added through a dropping funnel of which the exit tube dipsinto the reaction mixture. The ammonia is evaporated off, with stirring,until the temperature in the reaction vessel has risen to 40 C. Thetoluene is subsequently distilled off under reduced pressure. Theresidual lethoxy-8-( l-methoxyl-methylethoxy)-2,6-dimethylocta-2,6-dien-4-yn-3-ol is a light-brown oil.U.V. maximum [in ethanol]; 228 my; a 18000; n,,= L5 120; d l.002.

The 5-(lmethoxy-methylethoxy)-3-methyl-pent-3- en-l-yne employed asstarting compound can be manufactured as follows:

96 g. of 3-methyl-pent-2-en-4-yn-l-ol are, after the addition of 0.5 ml.of 10 per dent methyl alcoholic p toluenesulphonic acid, treated withstirring and cooling at 5 to 15 C. with 79 g. of isopropenyl methylether. The acetal is not isolated, but further processed directly.

B. Preparation of hydroxy compound.

270 g. of i-ethoxy-8-(lmethoxy-l-methylethoxy)-2,6-dimethyl-octa-2,6-dien-4-yn-3-ol are dissolved in 400 ml. of tolueneand, with cooling and strong stirring, treated with 50 ml. of 2 per.cent sulphuric acid and 50 ml. of methanol, in doing which thetemperature should not exceed 25 C. The reaction mixture is subsequentlystirred at 20 to 25 C. with nitrogen gassing for 2 hours. The toluenephase is separated, washed with 400 ml. of a 10 per cent aqueous sodiumsulphate solution and subsequently with 400 ml. of a 5 per cent sodiumdissolved in toluene obtained according to above is,

after the addition of 180 ml. of pyridine, treated with stirring at 0 to10 C. with ml. of acetyl chloride in ml. of toluene. After completion ofthe treatment, the reaction mixture is stirred at 20 to 25 C. for 30minutes and subsequently thoroughly shaken with 200 ml. of water. Thetoluene phase is separated and successively washed at 20 25 C. with 300ml. of'lOper cent aqueous sulphuric acid, 400 ml. of water and 200 ml.of water. The aqueous phase is separated and again shaken out twice with50 ml. of toluene each time. The combined toluene solutions areevaporated under reduced pressure at 60 C. The residual crude 2,6-

dimethyl-8-acetoxy-octa-2,6-dien-4-yn-1-a1 can be purifled bydistillation in high vacuum. The forerun going over at up to about 100C. [external temperature 120 C., internal pressure 0.03 Torr.) consistschiefly of 3- methyl-S-acetoxy-pent-3-en-1-yne. The pure 2,6-dimethyl-8-acetoxy-octa-2,6-dien-4-yn-1-a1 melts at 36 to 37 C.

D. Hydrogenation of Ester.

5.0 g. of 2,6-dimethy1-8-acetoxy-octa-2,6-dien-4-yn l-al are dissolvedin 30 m1. of toluene and, after the addition of 0.4 g. of apalladium/calcium carbonate catalyst deactivated by addition of lead andquinoline [He1v. Chim. Acta. 35 (1952), 446], hydrogenated up to theuptake of 1.05 equivalents of hydrogen. The reaction solution, afterseparation of the catalyst, is successively washed with 0.5-N sulphuricacid, potassium hydrogen carbonate solution and water, then dried oversodium sulphate and treated with a solution of 0.02 g. of iodine in 2ml. of toluene. The solution is allowed to stand at room temperature for18 hours and is subsequently successively washed with a 5 per centsodium thiosulphate solution and water, then dried over sodium sulphateand evaporated under reduced pressure. The residual2,6-dimethy1-8-acetoxy-octa- 2,4,6-trien-l-al melts at 70 to 72 C. afterrecrystallization from ethyl ether/petroleum ether [boiling range 30 to40 C.].

prepared in part B of Example 20 and was converted into2,6-dimethyl-8-hydroxy-octa-2,4,6-dien-al (1) by partial hydrogenationin the exact manner set forth in part D of Example 20.

EXAMPLE 22 This example is directed to preparing 6-hydroxy-4- methylhexadient(2,4)-a1-( 1) which is utilized as starting material in Example2.

A. Preparation of 6,6-diethoxy-3-methyl-hexen-(2)- yn-(4)-ol-(1).

To a Grignard solution (prepared from 61 g. of magnesium and 328 g. ofethyl bromide in 100* ml. of tetrahydrofuran and 100 ml. of benzene) wasadded at 0C within 20 minutes a solution of 112.5 g. oftrans-3-methyl-penten-(2)-yn-(4)-ol-( 1) in 400 ml. of benzene. The reactionmixture was kept-under reflux conditions for one hour. Within one hourand while stirring 180 g. of orthoformic acid triethyl ester were thenadded dropwise and the resulting mixture refluxed for 10 hours. Themixture was then poured into 2 kg. of ice and water and acidified to apH of 6 by the addition of acetic acid. The benzene phase was separatedand washed with water. After evaporation of the benzene there wasobtained 6,6-diethoxy-3-methyl-hexen-(2- yn(4)-ol-(1) of boiling pointll5/0.l mm; m, 1,4820; absorption maximum 225 my; E ,,,'=780.

B. Preparation of 6,6-diethoxy-3-methyl-hexadien- 39.6 g. of6,6-diethoxy-3-methyl-hexen-(2)-yn-(4)- ol-(l) were dissolved in 200 ml.of petroleum ether (boiling range 80-105) and 64 ml. of ethanol and,after the addition of 5,2 g. of a palladium/calcium carbonate catalystdeactivated by addition of lead and quinoline [Helv. Chim. Acta 35(1952), 446] and 6,4 ml. of B-pyridine-methanol, hydrogenated at 23C upto the uptake of 4.5 l. of hydrogen. After separation of the catalystand evaporation of the solvent, the residue was distilled in a highvacuum. There was obtained 6,6- diethoxy-3-methyl-hexadien-(2,4)-o1-(l)of boiling point 93-94C/0.02 mm; n 1,4777; absorption maximum 232 mu, E=6l7.

C. Preparation of 6-hydroxy-4-methyl-hexadien-(2,4

96 g. of 6,6-diethoxy-3-methyl-hexadien-(2,4)-ol-( l were dissolved in200 ml. of ether and treated with 100 ml. of 3N hydrochloric acid. Themixture was stirred at room temperature for 20 minutes and then treatedwith 20 g. of potassium carbonate. After filtration the filtrate wasconcentrated to l00 m1. and kept at -l5C overnight. The precipitationformed was separated, washed with cold ether and dried under reducedpressure at 35. There was obtained all-trans-6-hydroxy-4-methyl-hexadien-(2,4)-al-( l melting at 50-60. After recrystallizationfrom isopropyl ether the aldehyde melted at 65.566.5C.

EXAMPLE 23 This example is directed to the preparation of 8 acetoxy-l,1rdiethoxy-2,6-dimethyl-octadien-(2,6 yne-(4), which is utilized asstarting material in Example 3.

A solution of 1 ml. of85 percent phosphoric acid and 1 g. ofp-toluene-sulfonic acid in 75 ml. of absolute ethanol was dropped to amixture of 206 g. of 8-acetoxy-2,6-dimethyl-octadien-(2,6)-yn-(4)-al-(1)and g. of orthoformic acid triethyl ester, whereby the mixture wasstirred, and by occasional cooling it was taken care that the reactiontemperature did not exceed 30C. The mixture was maintained at roomtemperature for 3 hours, then cooled to 0C, treated with 30 g. of sodiumhydrogen carbonate'and stirred for 10 minutes. Additional 30 g. ofsodium hydrogen carbonate and 200 ml. of ice-water were then added andthe resulting mixture extracted with ether. The ether extract was washedtwice with ether, dried over potassium carbonate and concentrated invacuum. There was obtained 8-acetoxy-l l-diethoxy-2,6-dimethyl-octadien-(2,6 )-yn(4)-al- (l), boiling at 50/0.04mm; absorption m'axima: 263, 283 mu, E 810, 610.

CLAIMS:

l. A composition, comprising a material selected from the groupconsisting of foodstuffs, pharmaceuticals and cosmetics havingincorporated therein in an amount of 0.0000001 parts by weight to 0.1parts by weight ofa coloring agent selected from the group con sistingofcompounds having the formula:

wherein X is an integer from 0 to 1, Y is an integer from O to 3 withthe proviso that the sum of X and Y is an integer of at least one, andmixtures thereof. 7 2. The composition of claim 1 wherein said coloringagent is 4,9-dimethyl-dodeca-pentaene-(2,4,6,8,10)- dial-(1,12).

3. The composition of claim 1 wherein said coloring agent is2,6,l0,'l5,19,23-hexamethyl-tetracosa-undecacne-(2,4,6,8,l(),12,14,16,!8,20,22)-dial-(1,24).

4. The composition of claim 1 wherein said coloring agent is4,8,l2,l7,21,25-hexamethyl-octacsatridecaene-(2,4,6,8,l0,12,l4,l6,l8,20,22,24,26)-dial-(1,28).

5. The composition of claim 1 wherein said dialdehyde is 2,6,10,14, 19,23, 27, 3l-octamethyl-

1. A composition comprising a material selected from the groupconsisting of foodstuffs, pharmaceuticals and cosmetics havingincorporated therein in an amount of 0.0000001 parts by weight to 0.1parts by weight of a coloring agent selected from the group consistingof compounds having the formula:
 2. The composition of claim 1 whereinsaid coloring agent is 4,9-dimethyl-dodeca-pentaene-(2,4,6,8,10)-dial-(1,12).
 3. The compositionof claim 1 wherein said coloring agent is 2,6,10,15,19,23-hexamethyl-tetracosa-undecaene-(2,4,6,8,10,12,14,16,18,20,22)-dial-(1,24).
 4. The composition of claim 1 wherein saidcoloring agent is 4,8,12,17,21,25-hexamethyl-octacosa-tridecaene-(2,4,6,8,10,12,14,16,18,20,22,24,26)-dial-(1,28).
 5. The composition of claim 1 whereinsaid dialdehyde is 2,6,10, 14, 19, 23, 27,31-octamethyl-dotriacontapentadecaene-(2,4,6,8,10,12,14,16,18,20,22,24,26,28,30)-dial-(1,32).